Oxygen free deposition of platinum group metal films

ABSTRACT

Methods of depositing platinum group metal films of high purity, low resistivity, and good conformality are described. A platinum group metal film is formed in the absence of an oxidant. The platinum group metal film is selectively deposited on a conductive substrate at a temperature less than 200° C. by using an organic platinum group metal precursor.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/721,917, filed Aug. 23, 2018, the entire disclosure of which ishereby incorporated by reference herein.

TECHNICAL FIELD

Embodiments of the present disclosure pertain generally to filmdeposition. More particularly, embodiments of the disclosure providemethods for depositing platinum group metal films in the absence of anoxidant.

BACKGROUND

The semiconductor processing industry continues to strive for largerproduction yields while increasing the uniformity of layers deposited onsubstrates having larger surface areas. These same factors, incombination with new materials, also provide higher integration ofcircuits per unit area of the substrate. As circuit integrationincreases, the need for greater uniformity and process control regardinglayer thickness rises. As a result, various technologies have beendeveloped to deposit layers on substrates in a cost-effective manner,while maintaining control over the characteristics of the layer.

Chemical vapor deposition (CVD) is one of the most common depositionprocesses employed for depositing layers on a substrate. CVD is aflux-dependent deposition technique that requires precise control of thesubstrate temperature and the precursors introduced into the processingchamber in order to produce a desired layer of uniform thickness. Theserequirements become more critical as substrate size increases, creatinga need for more complexity in chamber design and gas flow technique tomaintain adequate uniformity.

A variant of CVD that demonstrates excellent step coverage is cyclicaldeposition or atomic layer deposition (ALD). Atomic layer deposition isbased upon atomic layer epitaxy (ALE) and employs chemisorptiontechniques to deliver precursor molecules on a substrate surface insequential cycles. The cycle exposes the substrate surface to a firstprecursor, a purge gas, a second precursor and the purge gas. The firstand second precursors react to form a product compound as a film on thesubstrate surface. The cycle is repeated to form the layer to a desiredthickness.

The advancing complexity of advanced microelectronic devices is placingstringent demands on currently used deposition techniques. Because oftheir high corrosion resistance, microelectronic devices having platinumgroup metals are desired in applications where great reliability isdesired and also where a corrosive atmosphere may be present. Existingplatinum group metal deposition requires an oxidation reactant. Theoxidation reactant diffuses through the deposited platinum group metalfilm, oxidizing the substrate and causing resistivity increases andadhesion deterioration. As a result, the device performance can beseriously compromised. Thus, there is a need for methods of depositingplatinum group metal films which do not result in damage to theunderlying substrate.

SUMMARY

Apparatuses and methods to manufacture integrated circuits aredescribed. In one or more embodiments, a method of depositing a film isdescribed. In an embodiment, the method comprises flowing an organicplatinum group metal precursor into a deposition chamber in the presenceof a reducing agent. The deposition chamber is substantially free of anoxidant. A platinum group metal film is then selectively deposited on aconductive substrate at a temperature less than 200° C.

In one or more embodiments, a method of depositing a film is described.The method comprises positioning a conductive substrate in a processingchamber. The conductive substrate is then exposed to an organic platinumgroup metal precursor to selectively deposit a platinum group metal filmon the conductive substrate at a temperature less than 200° C. Theprocessing chamber is purged of the organic platinum group metalprecursor. The conductive substrate is then exposed to a reducing agent,the processing chamber substantially free of an oxidant. The processingchamber is then purged of the reducing agent.

In one or more embodiments, an electronic device is described. Theelectronic device comprises a conductive substrate. At least one featureis formed in the conductive substrate. A platinum group metal film is onthe conductive substrate and is on the at least one feature. Theplatinum group metal film has an impurity of less than 5 atomic % and aresistivity less than 100 μΩ-cm.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentdisclosure can be understood in detail, a more particular description ofthe disclosure, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this disclosure and are therefore not to beconsidered limiting of its scope, for the disclosure may admit to otherequally effective embodiments. The embodiments as described herein areillustrated by way of example and not limitation in the figures of theaccompanying drawings in which like references indicate similarelements.

FIG. 1 depicts a flow process diagram of one embodiment of a method offorming a thin film according to embodiments described herein;

FIG. 2 illustrates a cross-sectional view of a substrate according toone or more embodiments;

FIG. 3 illustrates a cross-sectional view of a substrate according toone or more embodiments;

FIG. 4 is a block diagram of a process chamber in accordance with one ormore embodiment of the disclosure; and

FIG. 5 is a block diagram of a cluster tool system in accordance withone or more embodiment of the disclosure.

DETAILED DESCRIPTION

Before describing several exemplary embodiments of the disclosure, it isto be understood that the disclosure is not limited to the details ofconstruction or process steps set forth in the following description.The disclosure is capable of other embodiments and of being practiced orbeing carried out in various ways.

Embodiments of the disclosure provide processes for depositing platinumgroup metal films. The process of various embodiments uses vapordeposition techniques, such as an atomic layer deposition (ALD) orchemical vapor deposition (CVD) to provide platinum group metal films.One or more embodiments advantageously provide a method of depositing aplatinum group metal film on a conductive substrate, which deposition isconducted in the absence of an oxidant. The lack of an oxidantadvantageously results in a platinum group metal film having a lowimpurity level (e.g. less than 5 atomic % atomic), low resistivity (e.g.less than 100 μΩ-cm, including less than 90 μΩ-cm, less than 80 μΩ-cm,less than 70 μΩ-cm, less than 60 μΩ-cm, less than 50 μΩ-cm, less than 40μΩ-cm, less than 30 μΩ-cm, less than 20 μΩ-cm, or less than 10 μΩ-cm),high work function, good surface roughness when compared to theroughness of the conductive substrate prior to deposition, and goodconformality.

As used in this specification and the appended claims, the term“substrate” refers to a surface, or portion of a surface, upon which aprocess acts. It will also be understood by those skilled in the artthat reference to a substrate can refer to only a portion of thesubstrate, unless the context clearly indicates otherwise. Additionally,reference to depositing on a substrate can mean both a bare substrateand a substrate with one or more films or features deposited or formedthereon.

A “substrate” as used herein, refers to any substrate or materialsurface formed on a substrate upon which film processing is performedduring a fabrication process. For example, a substrate surface on whichprocessing can be performed include materials such as silicon, siliconoxide, strained silicon, silicon on insulator (SOI), carbon dopedsilicon oxides, amorphous silicon, doped silicon, germanium, galliumarsenide, glass, sapphire, and any other materials such as metals, metalnitrides, metal alloys, and other conductive materials, depending on theapplication. Substrates include, without limitation, semiconductorwafers. Substrates may be exposed to a pretreatment process to polish,etch, reduce, oxidize, hydroxylate (or otherwise generate or grafttarget chemical moieties to impart chemical functionality), annealand/or bake the substrate surface. In addition to processing directly onthe surface of the substrate itself, in the present disclosure, any ofthe film processing steps disclosed may also be performed on anunderlayer formed on the substrate as disclosed in more detail below,and the term “substrate surface” is intended to include such underlayeras the context indicates. Thus for example, where a film/layer orpartial film/layer has been deposited onto a substrate surface, theexposed surface of the newly deposited film/layer becomes the substratesurface. What a given substrate surface comprises will depend on whatmaterials are to be deposited, as well as the particular chemistry used.

A “conductive substrate” as used herein, refers to a substrate thatconducts electricity. Conductive substrates include conductor andsemiconductor materials.

A “non-conductive substrate” as used herein, refers to a substrate thatacts as an insulator.

In one or more embodiments, the substrate is a conductive substrate. Insome embodiments the conductive substrate is selected from a metal, ametal carbide, a metal nitride, or a metal silicide. The conductivesubstrate may comprise a metal selected from one or more of cobalt (Co),copper (Cu), nickel (Ni), ruthenium (Ru), manganese (Mn), silver (Ag),gold (Au), platinum (Pt), iron (Fe), molybdenum (Mo), rhodium (Rh),titanium (Ti), tantalum (Ta), silicon (Si), or tungsten (W). In one ormore specific embodiments, the metal substrate can comprise titaniumnitride (TiN) or tantalum nitride (TaN).

As used in this specification and the appended claims, the terms“precursor”, “reactant”, “reactive gas” and the like are usedinterchangeably to refer to any gaseous species that can react with thesubstrate surface.

“Atomic layer deposition” or “cyclical deposition” as used herein refersto the sequential exposure of two or more reactive compounds to deposita layer of material on a substrate surface. The substrate, or portion ofthe substrate, is exposed sequentially or separately to the two or morereactive compounds which are introduced into a reaction zone of aprocessing chamber. In a time-domain ALD process, exposure to eachreactive compound is separated by a time delay to allow each compound toadhere and/or react on the substrate surface and then be purged from theprocessing chamber. These reactive compounds are said to be exposed tothe substrate sequentially. In a spatial ALD process, different portionsof the substrate surface, or material on the substrate surface, areexposed simultaneously to the two or more reactive compounds so that anygiven point on the substrate is substantially not exposed to more thanone reactive compound simultaneously. As used in this specification andthe appended claims, the term “substantially” used in this respectmeans, as will be understood by those skilled in the art, that there isthe possibility that a small portion of the substrate may be exposed tomultiple reactive gases simultaneously due to diffusion, and that thesimultaneous exposure is unintended.

In one aspect of a time-domain ALD process, a first reactive gas (i.e.,a first precursor or compound A, e.g. organic platinum group metalprecursor) is pulsed into the reaction zone followed by a first timedelay. Next, a second precursor or compound B (e.g. reductant) is pulsedinto the reaction zone followed by a second delay. During each timedelay, a purge gas, such as argon, is introduced into the processingchamber to purge the reaction zone or otherwise remove any residualreactive compound or reaction by-products from the reaction zone.Alternatively, the purge gas may flow continuously throughout thedeposition process so that only the purge gas flows during the timedelay between pulses of reactive compounds. The reactive compounds arealternatively pulsed until a desired film or film thickness is formed onthe substrate surface. In either scenario, the ALD process of pulsingcompound A, purge gas, compound B, and purge gas is a cycle. A cycle canstart with either compound A or compound B and continue the respectiveorder of the cycle until achieving a film with the predeterminedthickness.

A “pulse” or “dose” as used herein is intended to refer to a quantity ofa source gas that is intermittently or non-continuously introduced intothe process chamber. The quantity of a particular compound within eachpulse may vary over time, depending on the duration of the pulse. Aparticular process gas may include a single compound or amixture/combination of two or more compounds, for example, the processgases described below.

The durations for each pulse/dose are variable and may be adjusted toaccommodate, for example, the volume capacity of the processing chamberas well as the capabilities of a vacuum system coupled thereto.Additionally, the dose time of a process gas may vary according to theflow rate of the process gas, the temperature of the process gas, thetype of control valve, the type of process chamber employed, as well asthe ability of the components of the process gas to adsorb onto thesubstrate surface. Dose times may also vary based upon the type of layerbeing formed and the geometry of the device being formed. A dose timeshould be long enough to provide a volume of compound sufficient toadsorb/chemisorb onto substantially the entire surface of the substrateand form a layer of a process gas component thereon.

The platinum group metal-containing process gas may be provided in oneor more pulses or continuously. The flow rate of the platinum groupmetal-containing process gas can be any suitable flow rate including,but not limited to, flow rates is in the range of about 1 to about 5000sccm, or in the range of about 2 to about 4000 sccm, or in the range ofabout 3 to about 3000 sccm or in the range of about 5 to about 2000sccm. The organic platinum group metal precursor of formula I can beprovided at any suitable pressure including, but not limited to, apressure in the range of about 5 mTorr to about 500 Torr, or in therange of about 100 mTorr to about 500 Torr, or in the range of about 5Torr to about 500 Torr, or in the range of about 50 mTorr to about 500Torr, or in the range of about 100 mTorr to about 500 Torr, or in therange of about 200 mTorr to about 500 Torr.

The period of time that the conductive substrate is exposed to theplatinum group metal-containing process gas may be any suitable amountof time necessary to allow the organic platinum group metal precursor toform an adequate nucleation layer atop the conductive substratesurfaces. For example, the process gas may be flowed into the processchamber for a period of about 0.1 seconds to about 90 seconds. In sometime-domain ALD processes, the platinum group metal-containing processgas is exposed the substrate surface for a time in the range of about0.1 sec to about 90 sec, or in the range of about 0.5 sec to about 60sec, or in the range of about 1 sec to about 30 sec, or in the range ofabout 2 sec to about 25 sec, or in the range of about 3 sec to about 20sec, or in the range of about 4 sec to about 15 sec, or in the range ofabout 5 sec to about 10 sec.

In some embodiments, an inert carrier gas may additionally be providedto the process chamber at the same time as the platinum groupmetal-containing process gas. The carrier gas may be mixed with theplatinum group metal-containing process gas (e.g., as a diluent gas) orseparately and can be pulsed or of a constant flow. In some embodiments,the carrier gas is flowed into the processing chamber at a constant flowin the range of about 1 to about 10000 sccm. The carrier gas may be anyinert gas, for example, such as argon, helium, neon, combinationsthereof, or the like. In one or more specific embodiments, the platinumgroup metal-containing process gas is mixed with argon prior to flowinginto the process chamber.

The temperature of the conductive substrate during deposition can becontrolled, for example, by setting the temperature of the substratesupport or susceptor. In some embodiments the conductive substrate isheld at a temperature less than about 200° C., including a temperatureless than about 190° C., less than about 180° C., less than about 170°C., less than about 160° C., less than about 150° C., less than about140° C., less than about 130° C., less than about 120° C., less thanabout 110° C., or less than about 100° C. In one or more embodiments,the substrate is maintained at a temperature in the range of about 100°C. to about 130° C.

In an embodiment of a spatial ALD process, a first reactive gas andsecond reactive gas (e.g., nitrogen gas) are delivered simultaneously tothe reaction zone but are separated by an inert gas curtain and/or avacuum curtain. The substrate is moved relative to the gas deliveryapparatus so that any given point on the substrate is exposed to thefirst reactive gas and the second reactive gas.

As will be understood by the skilled artisan, “chemical vapordeposition” refers to a process in which a substrate surface is exposedto precursors and/or co-reagents simultaneously or substantiallysimultaneously. As used herein, “substantially simultaneously” refers toeither co-flow or where there is overlap of exposures of the precursorsso that the reactive species are able to react in the gas phase.

In one or more embodiments, the platinum group metals which can bedeposited onto the surface of a conductive substrate include platinum(Pt), palladium (Pd), iridium (Ir), osmium (Os), ruthenium (Ru), andrhodium (Rh), or mixtures thereof. In one or more embodiments, theplatinum group metal film is one or more of a platinum group metalmetallic film, a platinum group metal carbide film, a platinum groupmetal nitride film, or a platinum group metal silicide film. Forexample, the platinum group metal film may be a platinum carbide film,or a platinum nitride film, or a platinum silicide film. In otherembodiment, the platinum group metal is a platinum group metal metallicfilm, and the platinum group metal consists essentially of platinum. Asused herein, the term “consists essentially of” means that thecomposition of the bulk film comprises the elements specified in a sumtotaling 95%, 98%, 99% or 99.5% of the total elemental composition on anatomic basis.

The platinum group metal film may be deposited by pulsing or coflowingan organic platinum group metal precursor containing the desiredplatinum group metal and a reducing agent (i.e. reactant) into a flowgas or carrier gas. As used herein, the term “carrier gas” refers to afluid (either gas or liquid) that can move a precursor molecule from onelocation to another. For example, a carrier gas can be a liquid thatmoves molecules from a solid precursor in an ampoule to an aerosolizer.In some embodiments, a carrier gas is an inert gas. In one or moreembodiments, a carrier gas is one or more of argon (Ar), helium (He),xenon (Xe), or nitrogen (N₂).

The organic platinum group metal precursor may be any suitable organiccompound which will allow the platinum group metal to deposit onto aconductive substrate under CVD or ALD conditions.

In one or more embodiments, the organic platinum group metal precursorhas a structure of general formula I:

wherein R¹ and R² are independently selected from C₁₋₄ alkyl, hydrogen,halogen, CO, and cyclopentadienyl; M is a platinum group metal; and L isa ligand comprising at least one carbon-carbon double bond, a (CH₂)_(x)where x is 1 to 8, and a NR³R⁴ where R³ and R⁴ are independentlyselected from C₁₋₄ alkyl, hydrogen, or halogen.

In one or more embodiments, the platinum group metal, M, is selectedfrom one or more of platinum (Pt), palladium (Pd), iridium (Ir), osmium(Os), ruthenium (Ru), or rhodium (Rh). As recognized by one skilled inthe art, the platinum group metal, M, may be a mixture of platinum groupmetals. For example, M may be a mixture of platinum (Pt) and palladium(Pd).

In one or more embodiments, L is a ligand. As used herein, the term“ligand” refers to an ion or molecule that binds to a metal atom forform a coordination complex. The bonding with the metal generallyinvolves donation of one or more of the ligand's electron pairs. L is aligand comprising at least one carbon-carbon double bond, a (CH₂)_(x)where x is 1 to 8, and a NR³R⁴ where R³ and R⁴ are independentlyselected from C₁₋₄ alkyl, hydrogen, or halogen. A carbon-carbon doublebond is a chemical bond between two carbon atoms involving four bondingelectrons. As used herein, the term alkylene group refers to the group(CH₂)_(x) where x may be from 1 to 8, including 1, 2, 3, 4, 5, 6, 7, or8. As used herein, the term amine refers to the group NR³R⁴, where thenitrogen atom is also bound to another group (e.g. (CH₂)_(x), alkylenegroup) in the ligand, L.

As used herein, “halogen” refers to one or more of a group of elementsin the periodic table, more particularly fluorine (F), chlorine (Cl),bromine (Br), iodine (I), and astatine (At).

As used herein, “alkyl,” or “alk” includes both straight and branchedchain hydrocarbons, containing 1 to 20 carbons, in the normal chain,such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl,pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl,2,2,4-trimethyl-pentyl, nonyl, decyl, undecyl, dodecyl, the variousbranched chain isomers thereof, and the like. Such groups may optionallyinclude up to 1 to 4 substituents. In one or more embodiments, each ofR¹ and R² are independently selected from C₁₋₄ alkyl, hydrogen, halogen,CO, and cyclopentadienyl. In one or more embodiments, each of R³ and R⁴are independently selected from C₁₋₄ alkyl, hydrogen, or halogen.

In one or more specific embodiments, the organic platinum group metalprecursor has a structure of general formula I:

wherein R¹ and R² are independently selected from C₁₋₄ alkyl, hydrogen,CO, and cyclopentadienyl; M is a platinum group metal; and L is a ligandR⁵NR³R⁴ where R³ and R⁴ are independently selected from C₁₋₄ alkyl orhydrogen, R⁵ is an alkenyl group comprising C_(n)H_(2n−1) or an alkynylgroup comprising C_(n)H_(2n−3) where n is from 3 to 8.

As used herein, “alkenyl,” includes both straight and branched chainhydrocarbons of 2 to 20 carbons, preferably 2 to 12 carbons, and morepreferably 1 to 8 carbons in the normal chain, which include one to sixdouble bonds in the normal chain, such as vinyl, 2-propenyl, 3-butenyl,2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl,3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl,4-dodecenyl, 4,8,12-tetradecatrienyl, and the like, and which may beoptionally substituted with 1 to 4 substituents, namely, halogen,haloalkyl, alkyl, alkoxy, alkenyl, alkynyl, aryl, arylalkyl, cycloalkyl,amino, hydroxy, heteroaryl, cycloheteroalkyl, alkanoylamino, alkylamido,arylcarbonyl-amino, nitro, cyano, thiol, alkylthio, and/or any of thealkyl substituents set out herein. In one or more embodiments thealkenyl group has from 3 to 8 carbon atoms.

In a specific embodiment, the carbon-carbon double bond is coordinatedto the platinum group metal, M. In a specific embodiment, the amine isdirectly bonded to the platinum group metal, M.

In one or more embodiments, the organic platinum group metal precursoris pulsed or coflowed with a reducing agent (i.e. reactant) into aprocessing chamber. The reducing agent may be any reducing agent knownto those of skill in the art of ALD and CVD film deposition. In one ormore embodiments, the reducing agent includes, but is not limited to,one or more of hydrogen (H₂), ammonia (NH₃), hydrazine (N₂H₄), silane(SiH₄), or disilane (Si₂H₆).

The organic platinum group metal precursor is pulsed or coflowed with areducing reactant into a processing chamber in the absence of anoxidant. The oxidant may be any oxidizing agent known to those of skillin the art of ALD and CVD film deposition. In one or more embodiments,the oxidant includes, but is not limited to, one or more of molecularoxygen (O₂), ozone (O₃), direct O₂ plasma, remote O₂ plasma, water(H₂O), or nitrogen oxides (e.g. NO, NO₂, N₂O, N₄O, N₂O₃, N₂O₄, N₂O₅,N₄O₆, and the like). Thus, in some embodiments, the processing chamberis devoid of water, oxygen, ozone, direct and remote O₂ plasma, nitrogenoxides, and the like. In other words, the processing chamber is not anoxidizing environment.

Without intending to be bound by theory, it is thought that an oxidantwill diffuse through the deposited platinum group metal film to oxidizethe underlying substrate, causing resistivity increases and adhesiondeterioration. As a result, the device performance, such as M cell or anon-volatile ferroelectric cell, can be seriously deteriorated.Accordingly, one or more embodiments provide a method of depositing aplatinum group metal film (e.g. platinum, platinum nitride, platinumsilicide, and the like) without using any oxidants.

The method of one or more embodiments provides for selective depositionof a platinum group metal (e.g. platinum, platinum nitride, platinumsilicide, platinum carbide, and the like) on a conductive substrate. Thedeposition of the platinum group metal is selective against depositionon a nonconductive substrate (e.g. SiO₂, silicon oxycarbide, siliconnitride, silicon carbonitride, titanium oxynitride, and the like). Inone or more embodiments, deposition using the organic platinum groupmetal precursor in combination with a reducing agent (i.e. reductant),and in the absence of an oxidant, provides a more selective platinumgroup metal film than a deposition using an oxidant (e.g. oxygen, water,etc.). As used herein, the term “selective” means that deposition of theplatinum group metal film on the conductive substrate occurs instead ofdeposition on a nonconductive substrate in a ratio greater than or equalto about 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1.100:1, 200:1, 300:1, 400:1, 500:1, 1000:1, or more.

Without intending to be bound by theory, it is thought that there is asynergistic relationship between the organic platinum group metalprecursor, reducing agent (i.e. reactant), and conductive substrate thatresults in the observed selectivity. This synergistic relationshipexists when the reaction is performed in the absence of an oxidant.

FIG. 1 depicts a flow diagram of a method 10 of depositing a film inaccordance with one or more embodiments of the present disclosure. Withreference to FIG. 1, the method 10 comprises a deposition cycle 70. Themethod 10 begins at operation 20 by positioning a conductive substrateinto a processing chamber.

The conductive substrate may be any conductive substrate known to one ofskill in the art. In one or more embodiments, the conductive substratecomprises a metal selected from one or more of cobalt (Co), copper (Cu),nickel (Ni), ruthenium (Ru), manganese (Mn), silver (Ag), gold (Au),platinum (Pt), iron (Fe), molybdenum (Mo), rhodium (Rh), titanium (Ti),tantalum (Ta), silicon (Si), or tungsten (W).

At operation 30, the conductive substrate is exposed in the processingchamber to the organic platinum group metal precursor to deposit aplatinum group metal-containing film.

At operation 40, the processing chamber is purged of the organicplatinum group metal precursor. Purging can be accomplished with anysuitable gas that is not reactive with the substrate, film on thesubstrate, and/or processing chamber walls. Suitable purge gasesinclude, but are not limited to, N₂, He, and Ar. The purge gas may beused to purge the processing chamber of the organometallic precursor,and/or the oxidant. In some embodiments, the same purge gas is used foreach purging operation. In other embodiments, a different purge gas isused for the various purging operations.

At operation 50, the conductive substrate is exposed to a reducing agentto react with the metal-containing film to form a platinum group metalfilm. In one or more embodiments, the reducing agent is selected fromone or more of hydrogen (H₂), ammonia (NH₃), hydrazine (N₂H₄), silane(SiH₄), or disilane (Si₂H₆). In one or more embodiments, the processingchamber is substantially free of an oxidant. As used herein, the term“substantially free” means that the processing chamber has less than 5.0wt. % oxidant, including less than 4.0 wt. % oxidant, less than 3.0 wt.% oxidant, less than 2.0 wt. % oxidant, less than 1.0% wt. % oxidant,and less than 0.5 wt. % oxidant.

In addition to the selectivity improvement, in one or more embodiments,using the organic platinum group metal precursor in combination with areducing agent in the absence of an oxidant, also advantageously offersunique film properties for the platinum group metal films. For example,the films prepared according to the methods of one or more embodiments,may have a roughness in a range of about 0.1 nm to about 3.0 nm. In oneor more embodiments, the films prepared have a rough that issubstantially the same as the roughness of the conductive substrateprior to deposition of the film. As used herein, the term “substantiallythe same” means that the roughness of the deposited film is less thanabout 5% of the roughness of the conductive substrate prior todeposition of the film, including less than about 4%, less than about3%, less than about 2%, or less than about 1%. The roughness of theplatinum group metal films is measured by atomic force microscopy (AFM).The films prepared according to one or more embodiments have a lowresistivity. More specifically, the resistivity of the platinum groupmetal films is less 100 μΩ-cm. The platinum group metal film of one ormore embodiments has an impurity of less than 5 atomic %. The platinumgroup metal films of one or more embodiments are high work functionmaterials and selective low resistivity etch stop layers. In one or moreembodiments, the platinum group metal film is selectively deposited on aconductive substrate to protect/stop the etching process before reachingthe underlying metal of the conductive substrate.

FIGS. 2-3 provide cross-sectional views according to one or moreembodiments. In one or more embodiments, the conductive substrate 102may be patterned according to any of the techniques known to those ofskill in the art. FIG. 2 is a cross-sectional view 100 of a conductivesubstrate 102 according to one or more embodiments. In one or moreembodiments, a conductive substrate 102 is provided and placed in aprocessing chamber 150. As used in this specification and the appendedclaims, the term “provided” means that the substrate is made availablefor processing (e.g., positioned in a processing chamber). Theconductive substrate 102 has a thickness T₁. In one or more embodiments,the conductive substrate 102 has a thickness T₁ of about 1 nm to about50 nm.

In one or more embodiments, the conductive substrate 102 comprises ametal selected from one or more of cobalt (Co), copper (Cu), nickel(Ni), ruthenium (Ru), manganese (Mn), silver (Ag), gold (Au), platinum(Pt), iron (Fe), molybdenum (Mo), rhodium (Rh), titanium (Ti), tantalum(Ta), silicon (Si), or tungsten (W). In one or more embodiments, theconductive substrate is one or more of a metal, a metal carbide, a metalnitride, or a metal silicide. In one or more specific embodiments, theconductive substrate 102 comprises or consists essentially of titaniumnitride.

FIG. 3 is a cross-sectional view 200 of a conductive substrate 102according to one or more embodiments. According to the method of one ormore embodiments, the conductive substrate 102 positioned in processingchamber 150 is exposed to an organic platinum group metal precursor todeposit a platinum group metal film 202 on the conductive substrate 102.

In one or more embodiments, the organic platinum group metal precursorhas a structure of general formula I:

wherein R¹ and R² are independently selected from C₁₋₄ alkyl, hydrogen,halogen, CO, and cyclopentadienyl; M is a platinum group metal; and L isa ligand comprising at least one carbon-carbon double bond, a (CH₂)_(x)where x is 1 to 8, and a NR³R⁴ where R³ and R⁴ are independentlyselected from C₁₋₄ alkyl or hydrogen.

In one or more embodiments, the platinum group metal film 202 comprisesa platinum group metal selected from the group consisting of platinum(Pt), palladium (Pd), iridium (Ir), osmium (Os), ruthenium (Ru), rhodium(Rh), and mixtures thereof. In one or more embodiments, the platinumgroup metal film is one or more of a platinum group metal metallic film,a platinum group metal carbide film, a platinum group metal nitridefilm, or a platinum group metal silicide film. In one or more specificembodiments, the platinum group metal consists essentially of platinum(Pt).

In one or more embodiments, exposing the conductive substrate 102 to anorganic platinum group metal precursor to deposit a platinum group metalfilm 202 involves an atomic layer deposition (ALD), which employssequential, self-limiting surface reactions to form the platinum groupmetal film 202. In one or more embodiments, an organic platinum groupmetal precursor is introduced into a processing chamber, where itpartially reacts with the surface of the conductive substrate 102. Then,a reductant is introduced to reduce the partially reacted precursor to aplatinum group metal film 202. In one or more embodiments, theprocessing chamber is free of an oxidant. As used herein, the term “freeof an oxidant” or “in the absence of an oxidant” means that there isless than about 5 wt. % oxidant present, including less than about 4.5wt. %, less than about 4.0 wt. %, less than about 3.5 wt. %, less thanabout 3.0 wt. %, less than about 2.5 wt. %, less than about 2.0 wt. %,less than about 1.5 wt. %, less than about 1.0 wt. %, less than about0.5 wt. %, less than about 0.25 wt. %, and less than about 0.1 wt. %.

In one or more embodiments, exposing the conductive substrate 102 to anorganic platinum group metal precursor to deposit a platinum group metalfilm 202 utlizes chemical vapor deposition (CVD), which involvesco-flowing an organic platinum group metal precursor and a reducingagent, in the absence of an oxidant, to form the platinum group metalfilm 202.

Reaction conditions, including temperature, pressure, processing time,the substrate surface(s), and the organic platinum group metalprecursors can be selected to obtain the desired level of selectivedeposition of the platinum group metal film 202 on the conductivesubstrate 102.

In one or more embodiments, the conductive substrate 102 is exposed tothe organic platinum group metal precursor at a temperature less thanabout 200° C. including a temperature less than about 190° C., less thanabout 180° C., less than about 170° C., less than about 160° C., lessthan about 150° C., less than about 140° C., less than about 130° C.,less than about 120° C., less than about 110° C., or less than about100° C. In one or more embodiments, the substrate is maintained at atemperature in the range of about 100° C. to about 130° C.

In one or more embodiments, the conductive substrate 102 is exposed tothe organic platinum group metal precursor for a period of time in therange of about 1 minute to about 30 minutes, including about 1 minute,about 5 minutes, about 10 minutes, about 15 minutes, about 20 minutes,about 25 minutes, and about 30 minutes.

One or more embodiments are directed to a method of depositing a film.In one or more embodiments, the method comprises providing a conductivesubstrate 102. The conductive substrate 102 is exposed to an organicplatinum group metal precursor in a processing chamber 150 to deposit afirst metal film (not shown) on the metal layer 106. The processingchamber 150 is purged of the organic platinum group metal precursor. Theconductive substrate 102 is exposed to a reducing reactant gas(reductant) in the absence of an oxidant to react to form a platinumgroup metal film 202 on the conductive substrate 102. The processingchamber 150 is then purged of reductant.

In one or more embodiments, purging the processing chamber comprisesflowing a purge gas over the conductive substrate. The purge gas may beselected from one or more of argon (Ar), nitrogen (N₂), or helium (He).

The method of one or more embodiments may be repeated more than once toprovide a platinum group metal film on a conductive substrate.

According to one or more embodiments, the substrate is subjected toprocessing prior to and/or after forming the layer. This processing canbe performed in the same chamber or in one or more separate processingchambers. In some embodiments, the substrate is moved from the firstchamber to a separate, second chamber for further processing. Thesubstrate can be moved directly from the first chamber to the separateprocessing chamber, or the substrate can be moved from the first chamberto one or more transfer chambers, and then moved to the separateprocessing chamber. Accordingly, the processing apparatus may comprisemultiple chambers in communication with a transfer station. An apparatusof this sort may be referred to as a “cluster tool” or “clusteredsystem”, and the like.

Generally, a cluster tool is a modular system comprising multiplechambers which perform various functions including substratecenter-finding and orientation, degassing, annealing, deposition and/oretching. According to one or more embodiments, a cluster tool includesat least a first chamber and a central transfer chamber. The centraltransfer chamber may house a robot that can shuttle substrates betweenand among processing chambers and load lock chambers. The transferchamber is typically maintained at a vacuum condition and provides anintermediate stage for shuttling substrates from one chamber to anotherand/or to a load lock chamber positioned at a front end of the clustertool. Two well-known cluster tools which may be adapted for the presentdisclosure are the Centura® and the Endura®, both available from AppliedMaterials, Inc., of Santa Clara, Calif. However, the exact arrangementand combination of chambers may be altered for purposes of performingspecific portions of a process as described herein. Other processingchambers which may be used include, but are not limited to, cyclicallayer deposition (CLD), atomic layer deposition (ALD), chemical vapordeposition (CVD), physical vapor deposition (PVD), etch, pre-clean,chemical clean, thermal treatment such as RTP, plasma nitridation,degas, orientation, hydroxylation and other substrate processes. Bycarrying out processes in a chamber on a cluster tool, surfacecontamination of the substrate with atmospheric impurities can beavoided without oxidation prior to depositing a subsequent film.

According to one or more embodiments, the substrate is continuouslyunder vacuum or “load lock” conditions, and is not exposed to ambientair when being moved from one chamber to the next. The transfer chambersare thus under vacuum and are “pumped down” under vacuum pressure. Inertgases may be present in the processing chambers or the transferchambers. In some embodiments, an inert gas is used as a purge gas toremove some or all of the reactants after forming the layer on thesurface of the substrate. According to one or more embodiments, a purgegas is injected at the exit of the deposition chamber to preventreactants from moving from the deposition chamber to the transferchamber and/or additional processing chamber. Thus, the flow of inertgas forms a curtain at the exit of the chamber.

During processing, the substrate can be heated or cooled. Such heatingor cooling can be accomplished by any suitable means including, but notlimited to, changing the temperature of the substrate support (e.g.,susceptor) and flowing heated or cooled gases to the substrate surface.In some embodiments, the substrate support includes a heater/coolerwhich can be controlled to change the substrate temperatureconductively. In one or more embodiments, the gases (either reactivegases or inert gases) being employed are heated or cooled to locallychange the substrate temperature. In some embodiments, a heater/cooleris positioned within the chamber adjacent the substrate surface toconvectively change the substrate temperature.

The substrate can also be stationary or rotated during processing. Arotating substrate can be rotated continuously or in discreet steps. Forexample, a substrate may be rotated throughout the entire process, orthe substrate can be rotated by a small amount between exposure todifferent reactive or purge gases. Rotating the substrate duringprocessing (either continuously or in steps) may help produce a moreuniform deposition or etch by minimizing the effect of, for example,local variability in gas flow geometries.

FIG. 4 shows a block diagram of a plasma system 800 to perform at leastsome of the method of one or more embodiments. The plasma system 800illustrated has a processing chamber 801. A movable pedestal 802 to holda substrate 803 that has been positioned in processing chamber 801.Pedestal 802 can comprise an electrostatic chuck (“ESC”), a DC electrodeembedded into the ESC, and a cooling/heating base. In an embodiment,pedestal 802 acts as a moving cathode. In an embodiment, the ESCcomprises an Al₂O₃ material, Y₂O₃, or other ceramic materials known toone of ordinary skill of electronic device manufacturing. A DC powersupply 804 can be connected to the DC electrode of the pedestal 802. Insome embodiments, the pedestal 802 includes a heater (not shown) that iscapable of raising the temperature of the substrate to the firsttemperature. While an electrostatic chuck is illustrated as the pedestal802, those skilled in the art will understand that this is merelyexemplary and other pedestal types are within the scope of thedisclosure.

As shown in FIG. 4, a substrate 803 can be loaded through an opening 808and placed on the pedestal 802. Plasma system 800 comprises an inlet toinput one or more process gases 812 through a mass flow controller 811to a plasma source 813. A plasma source 813 comprising a showerhead 814is coupled to the processing chamber 801 to receive one or more processgases 812 to generate plasma. Plasma source 813 is coupled to a RFsource power 810. Plasma source 813 through showerhead 814 generates aplasma 815 in processing chamber 801 from one or more process gases 812using a high frequency electric field. Plasma 815 comprises plasmaparticles, such as ions, electrons, radicals, or any combinationthereof. In an embodiment, power source 810 supplies power from about 50W to about 3000 W at a frequency from about 400 kHz to about 162 MHz togenerate plasma 815.

A plasma bias power 805 is coupled to the pedestal 802 (e.g., cathode)via a RF match 807 to energize the plasma. In an embodiment, the plasmabias power 805 provides a bias power that is not greater than 1000 W ata frequency between about 2 MHz to 60 MHz, and in a particularembodiment at about 13 MHz. A plasma bias power 806 may also beprovided, for example, to provide another bias power that is not greaterthan 1000 W at a frequency from about 400 kHz to about 60 MHz, and in aparticular embodiment, at about 60 MHz. Plasma bias power 806 and plasmabias power 805 are connected to RF match 807 to provide a dual frequencybias power. In an embodiment, a total bias power applied to the pedestal802 is from about 10 W to about 3000 W.

As shown in FIG. 4, a pressure control system 809 provides a pressure toprocessing chamber 801. The chamber 801 has one or more exhaust outlets816 to evacuate volatile products produced during processing in thechamber. In an embodiment, the plasma system 800 is an inductivelycoupled plasma (ICP) system. In an embodiment, the plasma system 800 isa capacitively coupled plasma (CCP) system.

In some embodiments, a control system 817 is coupled to the processingchamber 801. The control system 817 comprises a processor 818, atemperature controller 819 coupled to the processor 818, a memory 820coupled to the processor 818, and input/output devices 821 coupled tothe processor 818. The memory 820 can include one or more of transitorymemory (e.g., random access memory) and non-transitory memory (e.g.,storage).

In one embodiment, the processor 818 has a configuration to control oneor more of: exposing a substrate in the processing chamber to a hafniumprecursor; purging of a substrate in the processing chamber, exposing asubstrate in the processing chamber to a dopant precursor, or forming athin film comprising less than or equal to about 50 monolayers of HfO₂doped with a dopant on a substrate.

The control system 817 can be configured to perform at least some of themethods as described herein and may be either software or hardware or acombination of both. The plasma system 800 may be any type of highperformance processing plasma systems known in the art, such as but notlimited to an etcher, a cleaner, a furnace, or any other plasma systemto manufacture electronic devices.

FIG. 5 illustrates a system 900 that can be used to process a substrateaccording to one or more embodiment of the disclosure. The system 900can be referred to as a cluster tool. The system 900 includes a centraltransfer station 910 with a robot 912 therein. The robot 912 isillustrated as a single blade robot; however, those skilled in the artwill recognize that other robot 912 configurations are within the scopeof the disclosure. The robot 912 is configured to move one or moresubstrate between chambers connected to the central transfer station910.

At least one pre-clean chamber 920 is connected to the central transferstation 910. The pre-clean chamber 920 can include one or more of aheater, a radical source or plasma source. The pre-clean chamber 920 isin fluid communication with an activating agent. An exemplary pre-cleanchamber 920 is illustrated in FIG. 4 as a plasma system 800.

In some embodiments, there are two pre-clean chambers 920 connected tothe central transfer station 910. In the embodiment shown in FIG. 4, thepre-clean chambers 920 can act as pass through chambers between thefactory interface 905 and the central transfer station 910. The factoryinterface 905 can include one or more robot 906 to move substrate from acassette to the pre-clean chamber 920. The robot 912 can them move thesubstrate from the pre-clean chamber 920 to other chambers within thesystem 900.

A deposition chamber 930 can be connected to the central transferstation 910. The deposition chamber 930 comprising a pedestal to hold asubstrate. The deposition chamber 930 is in fluid communication with oneor more reactive gas sources to provide one or more flows of reactivegases to the deposition chamber 930. The reactive gases of thedeposition chamber include the molecule that can form the monolayer onthe substrate.

The deposition chamber 930 can be any suitable chamber that can providea flow of molecules and control the temperature of the substrate. Theplasma system 800 shown in FIG. 4 can also be used as the depositionchamber 930. The substrate can be moved to and from the depositionchamber 930 by the robot 912 passing through isolation valve 914.

A selective deposition chamber 940 can also be connected to the centraltransfer station 910. The selective deposition chamber 940 can be anysuitable deposition chamber including, but not limited to, CVD, ALD,PECVD, PEALD, or PVD chambers. In some embodiments, the selectivedeposition chamber 940 comprises an ALD chamber. The ALD chamber can bea time-domain chamber where the reactive gases are sequentially exposedto the substrate so that only one reactive gas is present in the chamberat any given time. In some embodiments, the ALD chamber is a spatial ALDchamber with the reactive gases are flowed into separate regions of theprocessing chamber at the same time and the reactive gases are separatedby a gas curtain to prevent gas phase reactions between the reactivegases. In a spatial ALD chamber, the substrate is moved between regionsof the processing chamber containing the various reactive gases todeposit a film.

Other process chambers can be connected to the central transfer station910. In the embodiment shown, an ashing chamber 960 is connected to thecentral transfer station 910 through isolation valve 914. The ashingchamber 960 can be any suitable chamber that can remove the thin filmafter selective deposition.

At least one controller 950 is coupled to the central transfer station910, the pre-clean chamber 920, the deposition chamber 930, theselective deposition chamber 940, or the ashing chamber 960. In someembodiments, there are more than one controller 950 connected to theindividual chambers or stations and a primary control processor iscoupled to each of the separate processors to control the system 900.The controller 950 may be one of any form of general-purpose computerprocessor, microcontroller, microprocessor, etc., that can be used in anindustrial setting for controlling various chambers and sub-processors.

The at least one controller 950 can have a processor 952, a memory 954coupled to the processor 952, input/output devices 956 coupled to theprocessor 952, and support circuits 958 to communication between thedifferent electronic components. The memory 954 can include one or moreof transitory memory (e.g., random access memory) and non-transitorymemory (e.g., storage).

The memory 954, or computer-readable medium, of the processor may be oneor more of readily available memory such as random access memory (RAM),read-only memory (ROM), floppy disk, hard disk, or any other form ofdigital storage, local or remote. The memory 954 can retain aninstruction set that is operable by the processor 952 to controlparameters and components of the system 900. The support circuits 958are coupled to the processor 952 for supporting the processor in aconventional manner. Circuits may include, for example, cache, powersupplies, clock circuits, input/output circuitry, subsystems, and thelike.

Processes may generally be stored in the memory as a software routinethat, when executed by the processor, causes the process chamber toperform processes of the present disclosure. The software routine mayalso be stored and/or executed by a second processor (not shown) that isremotely located from the hardware being controlled by the processor.Some or all of the method of the present disclosure may also beperformed in hardware. As such, the process may be implemented insoftware and executed using a computer system, in hardware as, e.g., anapplication specific integrated circuit or other type of hardwareimplementation, or as a combination of software and hardware. Thesoftware routine, when executed by the processor, transforms the generalpurpose computer into a specific purpose computer (controller) thatcontrols the chamber operation such that the processes are performed.

The disclosure is now described with reference to the followingexamples. Before describing several exemplary embodiments of thedisclosure, it is to be understood that the disclosure is not limited tothe details of construction or process steps set forth in the followingdescription. The disclosure is capable of other embodiments and of beingpracticed or being carried out in various ways.

EXAMPLES Example 1

An in situ titanium nitride substrate was positioned in the processingchamber. The titanium nitride substrate was exposed to an organicplatinum precursor in a carrier gas, Ar (g) at a temperature of about130° C. The processing chamber was purged of the organic platinumprecursor. The titanium nitride substrate was exposed to a reducingagent, H₂ (g). The processing chamber did not contain an oxidant. Theprocessing chamber was purged of the reducing agent, H₂ (g). A platinumfilm was deposited on the in situ titanium nitride (TiN) substrate. Theplatinum film provided greater than 95% step coverage for 30 Å on the insitu titanium nitride. The platinum film has resistivity of about 60μΩ-cm, and an impurity of less than 5 atomic %.

Example 2—Comparative

An aged/ex situ titanium nitride substrate was positioned in theprocessing chamber. The titanium nitride substrate was exposed to anorganic platinum precursor in a carrier gas, Ar (g) at a temperature ofabout 130° C. The processing chamber was purged of the organic platinumprecursor. The aged/ex situ titanium nitride substrate contained a layerof native oxide (i.e. the titanium had oxidized to titanium oxide). Theaged/ex situ titanium nitride substrate was exposed to a reducing agent,H₂ (g). The processing chamber was purged of the reducing agent, H₂ (g).A platinum film was deposited on the aged/ex situ titanium nitride (TiN)substrate. The aged/ex situ titanium nitride gave poor film deposition.

Example 3

An in situ titanium nitride substrate was positioned in the depositionchamber. An organic platinum precursor was flowed into the depositionchamber in the presence of a carrier gas, Ar (g), and a reducing agent,H₂ (g). The deposition chamber did not contain an oxidant and wasmaintained at a temperature of about 130° C. A platinum film wasdeposited on the in situ titanium nitride. The platinum film providedgreater than 95% step coverage for 30 Å on the in situ titanium nitride.The platinum film has resistivity of about 60 μΩ-cm and an impurity ofless than 5 atomic %.

Example 4—Comparative

An aged/ex situ titanium nitride substrate was positioned in thedeposition chamber. An organic platinum precursor was flowed into thedeposition chamber in the presence of a carrier gas, Ar (g), and areducing agent, H₂ (g). The deposition chamber was maintained at atemperature of about 130° C. A platinum film was deposited on theaged/ex situ titanium nitride (TiN) substrate. The aged/ex situ titaniumnitride gave poor film deposition.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the materials and methods discussed herein(especially in the context of the following claims) are to be construedto cover both the singular and the plural, unless otherwise indicatedherein or clearly contradicted by context. Recitation of ranges ofvalues herein are merely intended to serve as a shorthand method ofreferring individually to each separate value falling within the range,unless otherwise indicated herein, and each separate value isincorporated into the specification as if it were individually recitedherein. All methods described herein can be performed in any suitableorder unless otherwise indicated herein or otherwise clearlycontradicted by context. The use of any and all examples, or exemplarylanguage (e.g., “such as”) provided herein, is intended merely to betterilluminate the materials and methods and does not pose a limitation onthe scope unless otherwise claimed. No language in the specificationshould be construed as indicating any non-claimed element as essentialto the practice of the disclosed materials and methods.

Reference throughout this specification to “one embodiment,” “certainembodiments,” “one or more embodiments” or “an embodiment” means that aparticular feature, structure, material, or characteristic described inconnection with the embodiment is included in at least one embodiment ofthe disclosure. Thus, the appearances of the phrases such as “in one ormore embodiments,” “in certain embodiments,” “in one embodiment” or “inan embodiment” in various places throughout this specification are notnecessarily referring to the same embodiment of the disclosure.Furthermore, the particular features, structures, materials, orcharacteristics may be combined in any suitable manner in one or moreembodiments.

Although the disclosure herein has been described with reference toparticular embodiments, it is to be understood that these embodimentsare merely illustrative of the principles and applications of thepresent disclosure. It will be apparent to those skilled in the art thatvarious modifications and variations can be made to the method andapparatus of the present disclosure without departing from the spiritand scope of the disclosure. Thus, it is intended that the presentdisclosure include modifications and variations that are within thescope of the appended claims and their equivalents.

What is claimed is:
 1. A method of depositing a film, the methodcomprising: flowing an organic platinum group metal precursor into adeposition chamber in the presence of a reducing agent, wherein thedeposition chamber is substantially free of an oxidant, the organicplatinum group metal precursor has a structure of general formula I

wherein R¹ and R² are independently selected from C₁₋₄ alkyl, hydrogen,halogen, CO, and cyclopentadienyl; M is a platinum group metal; and L isa ligand comprising at least one carbon-carbon double bond, a (CH₂)_(x)where x is 1 to 8, and a NR³R⁴ where R³ and R⁴ are independentlyselected from C₁₋₄ alkyl, hydrogen, or halogen; and selectivelydepositing a platinum group metal film on a conductive substrate versusdeposition on a nonconductive substrate in a ratio greater than or equalto 5:1 at a temperature less than 200° C., the platinum group metal filmhaving a resistivity of less than 100 μΩ-cm and an impurity of less than5 atomic %.
 2. The method of claim 1, wherein the platinum group metalis selected from the group consisting of platinum (Pt), palladium (Pd),iridium (Ir), osmium (Os), ruthenium (Ru), rhodium (Rh), and mixturesthereof.
 3. The method of claim 2, wherein the platinum group metalconsists essentially of platinum (Pt).
 4. The method of claim 1, whereinthe reducing agent is selected from one or more of hydrogen (H₂),ammonia (NH₃), hydrazine (N₂H₄), silane (SiH₄), or disilane (Si₂H₆). 5.The method of claim 1, wherein the platinum group metal film is one ormore of a platinum group metal metallic film, a platinum group metalcarbide film, a platinum group metal nitride film, or a platinum groupmetal silicide film.
 6. The method of claim 1, wherein the conductivesubstrate comprises a metal selected from one or more of cobalt (Co),copper (Cu), nickel (Ni), ruthenium (Ru), manganese (Mn), silver (Ag),gold (Au), platinum (Pt), iron (Fe), molybdenum (Mo), rhodium (Rh),titanium (Ti), tantalum (Ta), silicon (Si), or tungsten (W).
 7. Themethod of claim 6, wherein the conductive substrate is one or more of ametal, a metal carbide, a metal nitride, or a metal silicide.
 8. Amethod of depositing a film, the method comprising: positioning aconductive substrate in a processing chamber; exposing the conductivesubstrate to an organic platinum group metal precursor to selectivelydeposit a platinum group metal film on the conductive substrate versusdeposition on a nonconductive substrate in a ratio of greater than orequal to 5:1 at a temperature less than 200° C., the organic platinumgroup metal precursor having a structure of general formula I

wherein R¹ and R² are independently selected from C₁₋₄ alkyl, hydrogen,halogen, CO, and cyclopentadienyl; M is a platinum group metal; and L isa ligand comprising at least one carbon-carbon double bond, a (CH₂)_(x)where x is 1 to 8, and a NR³R⁴ where R³ and R⁴ are independentlyselected from C₁₋₄ alkyl, hydrogen, or halogen; purging the processingchamber of the organic platinum group metal precursor; exposing theconductive substrate to a reducing agent, the processing chambersubstantially free of an oxidant; and purging the processing chamber ofthe reducing agent, wherein the platinum group metal film has aresistivity of less than 100 μΩ-cm and an impurity of less than 5 atomic%.
 9. The method of claim 8, wherein the platinum group metal isselected from the group consisting of platinum (Pt), palladium (Pd),iridium (Ir), osmium (Os), ruthenium (Ru), and rhodium (Rh).
 10. Themethod of claim 8, wherein the reducing agent is selected from one ormore of hydrogen (H₂), ammonia (NH₃), hydrazine (N₂H₄), silane (SiH₄),or disilane (Si₂H₆).
 11. The method of claim 8, wherein the platinumgroup metal film is one or more of a platinum group metal metallic film,a platinum group metal carbide film, a platinum group metal nitridefilm, or a platinum group metal silicide film.
 12. The method of claim8, wherein the conductive substrate comprises a metal selected from oneor more of cobalt (Co), copper (Cu), nickel (Ni), ruthenium (Ru),manganese (Mn), silver (Ag), gold (Au), platinum (Pt), iron (Fe),molybdenum (Mo), rhodium (Rh), titanium (Ti), tantalum (Ta), silicon(Si), or tungsten (W).
 13. The method of claim 8, wherein purging theprocessing chamber comprises flowing a purge gas over the conductivesubstrate.
 14. The method of claim 8, wherein the purge gas is selectedfrom one or more of argon (Ar), nitrogen (N₂), or helium (He).